Enabling 100C Fast-Charging Bulk Bi Anodes for Na-Ion Batteries

It is challenging to develop alloying anodes with ultrafast charging and large energy storage using bulk anode materials because of the difficulty of carrier-ion diffusion and fragmentation of the active electrode material. Herein, a rational strategy is reported to design bulk Bi anodes for Na-ion batteries that feature ultrafast charging, long cyclability, and large energy storage without using expensive nanomaterials and surface modifications. It is found that bulk Bi particles gradually transform into a porous nanostructure during cycling in a glyme-based electrolyte, whereas the resultant structure stores Na ions by forming phases with high Na diffusivity. These features allow the anodes to exhibit unprecedented electrochemical properties; the developed Na–Bi half-cell delivers 379 mA h g⁻¹ (97% of that measured at 1C) at 7.7 A g⁻¹ (20C) during 3500 cycles. It also retained 94% and 93% of the capacity measured at 1C even at extremely fast-charging rates of 80C and 100C, respectively. The structural origins of the measured properties are verified by experiments and first-principles calculations. The findings of this study not only broaden understanding of the underlying mechanisms of fast-charging anodes, but also provide basic guidelines for searching battery anodes that simultaneously exhibit high capacities, fast kinetics, and long cycling stabilities.